Sulfonated polyester-siloxane resin

ABSTRACT

A toner comprised of colorant and a sulfonated polyester-siloxane polymer generated from the reaction of at least one organic diol monomer, at least one organic diacid or at least one diester monomer, at least one carbinol carboxy terminated polydimethyl siloxane, and at least one ion salt of a sulfonate difunctional monomer.

CROSS REFERENCE

Illustrated in copending application U.S. Ser. No. 10/170,993, filedJun. 12, 2002, the disclosure of which is totally incorporated herein byreference, is a sulfonated polyester siloxane polymer generated from thereaction of at least one organic diol monomer, at least one organicdiacid monomer or at least one diester monomer, at least one carbinolcarboxy terminated polydimethylsiloxane, and at least one ion salt of asulfonate difunctional monomer.

BACKGROUND

The present invention is generally directed to polymer components, andmore specifically, the present invention is directed to a resincomprised of a polyester-siloxane copolymer backbone with an ionichydrogen sulfonate, a hydrophilic hydrogen sulfonate, or a metalizedsulfonate group, and wherein the metal is, for example, zinc, copper,manganese, chromium, iron, zirconium or an alkali metal such as sodium,lithium, potassium, rubidium cesium, beryllium, magnesium, calcium,strontium, barium, and/or mixtures thereof. More specifically, the resincomposition is comprised of a hydrogen or metalizedsulfo-polyester-siloxane copolymer of the formula

wherein the segments m, n and o represent the random units of thepolymer or resin, and wherein the sum of m, n, and o are, for example,from about 10 to about 10,000, and more specifically, from about 100 toabout 5,000, and yet more specifically, from about 1,000 to about 4,000,and p represents the repeating segment of the polydimethylsiloxane andis, for example, from about 100 to about 10,000, more specifically fromabout 100 to about 7,000, and yet more specifically, from about 1,000 toabout 5,000 units; and wherein R is an alkylene with, for example, fromabout 1 to about 16 carbon atoms, such as ethylene, propylene, butylene,pentylene, hexylene, octylene, 1,2-propylene, cyclohexanedimethylene,and the like; an oxyalkylene containing, for example, from about 4 toabout 30 carbon atoms, such as diethylene glycol or dipropyleneglycol;an arylene radical or group with, for example, from about 6 to about 36carbon atoms, such as benzylene, 1,4-phenylene, 1,3-phenylene,1,2-phenylene, or anthracylene; and R′ is an alkali arylenesulfonatewith, for example, from about 6 to about 30 carbon atoms, such asphenylenesulfonate, isophthalylene-5-sulfonate,terephthalylene-sulfonate phthalylene-sulfonate; an alkalialkylene-sulfonate, such as propylene-sulfonate, butylene-sulfonate,pentylene-sulfonate, hexylene-sulfonate of, for example, the followingformulas

wherein a and b are numbers of from about 1 to about 5, and M ishydrogen, an alkali (I) metal, such as lithium, sodium, potassium,rubidium, cesium, or an alkali (II) metal, such as beryllium, magnesium,calcium, strontium or barium, or a metal, such as zinc (II), iron (III),aluminum (III), or copper (I); and R″ is an alkylene, such as ethylene,propylene or butylene.

Moreover, in embodiments the sulfopolyester-siloxane copolymer can bewater dissipatible thereby providing a readily available emulsion inwater. In embodiments the resins or polymers illustrated herein can beselected for paints, toners, or protective coatings for the protectionof substrates from corrosion, oxidative aging, mechanical damage orweathering, such as a coating for textiles, paper, wood, leather, glass,ceramics, porcelain, metal, plastics, stone, concrete, or metalsurfaces, and especially wherein water dispersible resin coatings withslip resistance is desired.

REFERENCES

Certain sulfonated polyester resins are known, reference for exampleU.S. Pat. No. 3,018,272, the disclosure of which is totally incorporatedherein by reference, wherein a variety of sulfoacids and metalizedsulfonates are incorporated into a polyester resin. In U.S. Pat. No.3,563,942, the disclosure of which is totally incorporated herein byreference, there are disclosed linear solvent soluble copolyestercompositions that can be dispersed in water. Water dispersibility can beachieved, it is believed, by the addition to the copolyester of a smallamount (1-2 mole percent) of a metal salt of a sulfonated aromaticcompounds. Water dispersible or dissipatible polyester resins are alsoknown, such as those disclosed in U.S. Pat. No. 3,734,874, thedisclosure of which is totally incorporated herein by reference, andwherein these sulfonated polyester resins can be derived from apolyethylene glyco and dicarboxylic acid metal salts of5-sulfoisophthalic acid. U.S. Pat. No. 4,340,519, the disclosure ofwhich is totally incorporated herein by reference, discloses certaincrystalline and noncrystalline polyesters copolymerized with a metalsulfonate group containing aromatic acid and up to 10 mole percent(based on the total polyol content) of a polyvalent polyol selected fromtrimethylolpropane, trimethylolethane, glycerine, and pentaerythritol.Also, U.S. Pat. No. 4,525,524, the disclosure of which is totallyincorporated herein by reference, discloses liquid systems comprised ofpolyester containing certain metal sulfonates and, optionally, up to 3percent of a branching agent based upon the total diol component.

Other water dispersible polyester based resins comprised of hydrophilicmoieties, such as alkali sulfonate groups, are disclosed, for example,in U.S. Pat. Nos. 5,348,832; 5,593,807; 5,604,076; 5,648,193; 5,658,704;5,660,965; 5,684,063; and 5,698,223, the disclosures of which are eachtotally incorporated herein by reference. The aforementioneddissipatible polyester resins usually contain hydrophilic moieties in anamount of from about 2 to about 7.5 percent by weight of resin.

Polyester-siloxane copolymers are also known, such as those disclosed inU.S. Pat. No. 4,465,712, the disclosure of which is totally incorporatedherein by reference, and wherein a siloxane-polyester compositioncomprised of the siloxane-polyester copolymer indicated are useful forthe coating of substrates, such as metals and plastics. In U.S. Pat. No.5,932,677, the disclosure of which is totally incorporated herein byreference, there is illustrated a thermoplastic condensation polymerwhich are terpolymers containing an aromatic polyester, a polysiloxaneand a polycarbonate segment.

In U.S. Pat. No. 5,466,554, the disclosure of which is totallyincorporated herein by reference, there is disclosed, for example, atoner comprised of a pigment, an optional charge enhancing additive,optional wax, and a polyester resin containing a hydrophobic end groupcomprised of a siloxane copolymer. In U.S. Pat. No. 5,354,815, thedisclosure of which is totally incorporated herein by reference, thereare disclosed polymers with enhanced hydrophilicity and thermalregulative properties; exemplary polymers include aliphatic polyamidepolymers and polyester polymers. The polymer has bonded thereto ahydrophilic polysiloxane having an affinity for the polymer and with amolecular weight greater than about 1,000 g/mol, more specifically,greater than about 2,000 g/mol, and yet more specifically, greater thanabout 4,000 g/mol.

Furthermore, in U.S. Pat. No. 5,262,492, the disclosure of which istotally incorporated herein by reference, there is disclosed asiloxane-modified polyester resin. These resins can comprise a copolymerof a siloxane compound, which contains at least one active hydrogenatom, and a lactone compound. The resulting copolymer is substantiallyfree of unreacted siloxane compound.

Processes for the preparation of certain siloxane-modified polyesterresins are known, such as those illustrated in U.S. Pat. No. 4,945,147,the disclosure of which is totally incorporated herein by reference, andwherein there can be accomplished the condensation of atetramethyldisiloxane bisbenzoic acid or an acid chloride with adihydric phenol, such as bisphenol A, with a mixture oftetramethyldisiloxane bisbenzoic acid and aromatic acids, such asterephthalic acid or isophthalic acid.

There are illustrated in U.S. Pat. No. 5,929,160, the disclosure ofwhich is totally incorporated herein by reference, certainwater-dispersible sulfopoly(ester-urethane) compositions comprising, intheir backbone, at least one non-terminally disposed arylene or alkylenegroup comprising a pendant sulfonic acid group or salt thereof, thepolymer being terminated by at least one hydrolyzable silyl group suchas 3-amino propyltriethoxysilane.

SUMMARY

It is a feature of the present invention to provide novel hydrogen ormetalized sulfo-polyester-siloxane resin compositions.

In another feature of the present invention there are providedpolyester-siloxane copolymer backbones with an ionic or hydrophilichydrogen sulfonate group.

In yet another feature of the present invention there are providedpolyester-siloxane copolymer backbones containing an ionic metalizedsulfonate group, and wherein the metal is, for example, zinc, copper,manganese, chromium, iron, zirconium or an alkali metal, such as sodium,lithium, potassium, rubidium cesium, beryllium, magnesium, calcium,strontium, barium or mixtures thereof.

Moreover, in another feature of the present invention there are providedwater emulsions comprised of a hydrogen or metalizedsulfo-polyester-siloxane resin and water.

Also, in another feature of the present invention there are providedtoner compositions comprised of a hydrogen or metalizedsulfo-polyester-siloxane resin, a colorant, and optionally a wax and/orflow additives.

Additionally, further features disclosed include providing toners withlow melting fusing characteristics, such as from about 120° C. to about145° C., broad fusing latitudes, such as from about 30° C. to about 70°C., and excellent charging characteristics; providing metalizedsulfo-polyester-siloxane resins with broad, such as about 50° C. toabout 65° C. glass transition temperatures, broad molecular weightranges, and excellent softening points; providing hydrogen and metalizedsulfo-polyester-siloxane resin emulsions with from about 10 to about 35percent solids loading in water for use as coatings; and providing ahydrogen and metalized sulfo-polyester-siloxane resin emulsion for useas a coating on paper, such as for example, to provide paper with aglossy coating and which paper can be useful as a photopaper.

EMBODIMENTS

Disclosed is a sulfonated polyester siloxane polymer generated from thereaction of at least one organic diol monomer, at least one organicdiacid monomer or at least one diester monomer, at least one carbinolcarboxy terminated polydimethylsiloxane, and at least one ion salt of asulfonate difunctional monomer; a sulfonated polyestersiloxane polymer,which polymer is represented by the following randomly chemicallyattached segments

wherein the segments m, n and o represent the random units of thepolymer, and wherein the sum of m, n, and o is from about 10 to about10,000; p represents the repeating segment of the polydimethylsiloxaneand is from about 100 to about 10,000 units; R is an alkylene; R′ is ahydrogen atom, an alkali arylenesulfonate or an alkalialkylene-sulfonate, and R″ is an alkylene; a polymer wherein thealkylene contains from about 1 to about 18 carbon atoms; and theoxyalkylene possesses a carbon chain length of from about 2 to about 36carbon atoms; a polymer wherein R′ is an alkali arylenesulfonate or analkali alkylene-sulfonate of the formulas

wherein a and b are numbers of from about 1 to about 5, and M ishydrogen, an alkali metal of lithium, sodium, potassium, rubidium,cesium, beryllium, magnesium, calcium, strontium and barium, or a metalof zinc (II), iron (III), aluminum (III), or copper (I); a polymerwherein the ion salt of the sulfonate difunctional monomer is thehydrogen, lithium, sodium, potassium, cesium, rubidium, magnesium,barium, calcium or beryllium, zinc, zirconium, vanadium, copper, oraluminum salt of dimethyl-5-sulfo-isophthalate,dialkyl-5-sulfo-isophthalate-4-sulfo-1,8-naphthalic anhydride,4-sulfo-phthalic acid, 4-sulfophenyl-3,5-dicarbomethoxybenzene,6-sulfo-2-naphthyl-3,5-dicarbomethoxybenzene, sulfo-terephthalic acid,dimethyl-sulfo-terephthalate, dialkyl-sulfo-terephthalate,sulfo-ethanediol, 2-sulfo-propanediol, 2-sulfo-butanediol,3-sulfo-pentanediol, 2-sulfo-hexanediol, 3-sulfo-2-methylpentanediol,N,N-bis(2-hydroxyethyl)-2-aminoethane sulfonate,2-sulfo-3,3-dimethylpentanediol, or sulfo-p-hydroxybenzoic acid; apolymer wherein the organic diol is ethylene glycol, 1,2-propyleneglycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol,1,4-butylene glycol, 1,2-pentylene glycol, 1,3-pentylene glycol,1,4-pentylene glycol, 1,5-pentylene glycol, 1,2-hexylene glycol,1,3-hexylene glycol, 1,4-hexylene glycol, 1,5-hexylene glycol,1,6-hexylene glycol, heptylene glycols, octylene glycols, decyleneglycol, dodecylene glycol, 2,2-dimethyl propanediol, propoxylatedbisphenol A, ethoxylated bisphenol A, 1,4-cyclohexane diol,1,3-cyclohexane diol, 1,2-cyclohexane diol, 1,2-cyclohexane dimethanol,or mixtures thereof, and optionally which glycols are selected in anamount of from about 45 to about 55 mole percent of the polymer product;a polymer wherein the organic diacid or diester is malonic acid,succinic acid, 2-methylsuccinic acid, 2,3-dimethylsuccinic acid,dodecylsuccinic acid, glutaric acid, adipic acid, 2-methyladipic acid,pimelic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalicacid, phthalic acid, 1,2-cyclohexanedioic acid, 1,3-cyclohexanedioicacid, 1,4-cyclohexanedioic acid, glutaric anhydride, succinic anhydride,dodecylsuccinic anhydride, maleic anhydride, fumaric acid, maleic acid,itaconic acid, 2-methyl itaconic acid, dialkyl esters of the diacids andthe dianhydrides, and wherein each is selected in an amount of fromabout 45 to about 55 mole percent of the polymer product; a polymerwherein the carbinol or carboxy terminated polydimethylsiloxanebis-(1,3-hydroxypropyl)-polydimethylsiloxane,bis-(1,3-hydroxyethyl)-polydimethylsiloxane, andbis-(1,3-hydroxybutyl)-polydimethylsiloxane, or carboxyl terminatedpolydimethyl siloxane, such asbis-(1,3-carboxypropyl)-polydimethylsiloxane,bis-(1,3-carboxyethyl)-polydimethylsiloxane, and selected in an amountof from about 5 mole percent to about 30 mole percent based on thestarting diacid or diester used to prepare the polymer; a polymer(siloxane) which possesses a number average molecular weight of fromabout 2,000 grams per mole to about 100,000 grams per mole, a weightaverage molecular weight of from about 4,000 grams per mole to about250,000 grams per mole, and a polydispersity of from about 1.8 to about17; a polymer which possesses a softening point of from about 20° C. toabout 150° C.; a polymer wherein the polymer disperses, dissipates oremulsifies in water at a temperature of from about 20° C. to about 100°C. to thereby provide a waterborne emulsion; a polymer wherein thepolymer exists as a waterborne emulsion with a solids content of fromabout 1 to about 35 percent by weight with the remainder being water; apolymer wherein the polymer exists as a waterborne emulsion and whereinthe polymer emulsion size diameter is from about 1 nanometer to about100 microns in size; a polymer as represented by the followingchemically bonded random segments

wherein the segments m, n and o represent the random units of thepolymer and wherein the sum of m, n, and o is from about 500 to about4,000; p represents the repeating segment of the polydimethylsiloxaneand is from about 1,000 to about 7,000 units; R is an alkylene; R′ is analkali arylenesulfonate of phenylenesulfonate,isophthalylene-5-sulfonate, terephthalylene-sulfonate,phthalylene-sulfonate, or an alkali alkylene-sulfonate ofpropylene-sulfonate, butylenes-sulfonate, pentylene-sulfonate, orhexylene-sulfonate of the formulas

wherein a and b are numbers of from about 1 to about 4, and M ishydrogen, an alkali (I) metal of lithium, sodium, potassium, rubidium,cesium, or an alkali (II) metal of beryllium, magnesium, calcium,strontium or barium or a metal of (II), iron (III), aluminum (III), orcopper (I), and R″ is ethylene, propylene or butylene derived from atleast one organic diol monomer, at least one organic diacid or diestermonomer, at least one carbinol or carboxy terminatedpolydimethylsiloxane, and at least an ion salt of the sulfonatedifunctional monomer; a polymer wherein the polyester siloxane isselected from the group consisting of copoly(dipropyleneterephthalate-co-diethylene terephthalate)-copoly(dipropylene5-sulfoisophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethylsiloxane, copoly(1,2-propyleneterephthalate-)-copoly(1,2-propylene5-sulfoisophthalate)-copolydimethylsiloxane, copoly(dipropyleneterephthalate)-copoly(dipropylene 5-sulfoisophthalate)-copolydimethylsiloxane, copoly(ethylene terephthalate)-copoly(ethylene5-sulfoisophthalate)-copolydimethylsiloxane, copoly(butylleneterephthalate)-copoly(butyllene5-sulfoisophthalate)-copolydimethylsiloxane, and copoly(1,3-propyleneterephthalate)-copoly(1,3-propylene5-sulfoisophthalate)-copolydimethylsiloxane; a polymer wherein thepolyester siloxane is copoly(1,2-propylene terephthalate-co-diethyleneterephthalate)-copoly(1,2-propylene 5-sulfoisophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethylsiloxane; a polymer wherein theorganic diacid or diester is terephthalic acid or dimethylterephthalate; a sulfonated polyester siloxane copolymer resin generatedfrom the reaction of at least one organic diol monomer, at least oneorganic diacid monomer, at least one carbinol carboxy terminatedpolydimethyl siloxane, and at least one ion salt of a sulfonatedifunctional monomer; a sulfonated polyester siloxane copolymer resingenerated from the reaction of at least one organic diol monomer, atleast one organic diester monomer, at least one carbinol carboxyterminated polydimethyl siloxane, and at least one ion salt of asulfonate difunctional monomer, and optionally wherein at least one isfrom about 1 to about 7; a polymer wherein the alkylene is ethylene,propylene, butylenes, pentylene, hexylene, heptylene, or octylene; apolymer wherein at least one is from 1 to about 25; a polymer wherein atleast one is from 1 to about 10; a polymer wherein at least one is from1 to about 5, and there is selected an organic diacid monomer; a polymerwherein at least one is 1; a polymer wherein there is selected anorganic diester monomer; a toner comprised of colorant and a sulfonatedpolyester-siloxane polymer generated from the reaction of at least oneorganic diol monomer, at least one organic diacid or at least onediester monomer, at least one carbinol carboxy terminated polydimethylsiloxane, and at least one ion salt of a sulfonate difunctional monomer;a toner wherein the colorant is a pigment; a toner wherein the colorantis a dye; a toner wherein the colorant is comprised of a mixture of apigment and a dye; a toner wherein the polymer contained therein iscopoly(1,2-propylene terephthalate-co-diethyleneterephthalate)-copoly(1,2-propylene 5-sulfoisophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethylsiloxane, copoly(dipropyleneterephthalate-co-diethylene terephthalate)-copoly(dipropylene5-sulfoisophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethylsiloxane, copoly(1,2-propyleneterephthalate)-copoly(1,2-propylene5-sulfoisophthalate)-copolydimethylsiloxane, or copoly(dipropyleneterephthalate)-copoly(dipropylene5-sulfoisophthalate)-copolydimethylsiloxane; a toner comprised of apolymer represented by the following randomly chemically attachedsegments

wherein the segments m, n and o represent the random units of thepolymer and wherein the sum of m, n, and o is from about 10 to about10,000; p represents the repeating segment of the polydimethyl siloxane,and is from about 100 to about 10,000 units; R is an alkylene; R′ is ahydrogen atom, an alkali arylenesulfonate or an alkalialkylene-sulfonate, and R″ is an alkylene; a toner wherein the alkylenecontains from about 1 to about 18 carbon atoms; and the oxyalkylenepossesses a carbon chain length of from about 2 to about 36 carbonatoms; a toner wherein R′ is an alkali arylene sulfonate or an alkalialkylene sulfonate of the formulas

wherein a and b are numbers of from about 1 to about 5, and M ishydrogen, an alkali metal of lithium, sodium, potassium, rubidium,cesium, beryllium, magnesium, calcium, strontium and barium, or a metalof zinc (II), iron (III), aluminum (III), or copper (I); a toner whereinthe ion salt of the sulfonate difunctional monomer is the hydrogen,lithium, sodium, potassium, cesium, rubidium, magnesium, barium, calciumor beryllium, zinc, zirconium, vanadium, copper, or aluminum salt ofdimethyl-5-sulfo-isophthalate,dialkyl-5-sulfo-isophthalate-4-sulfo-1,8-naphthalic anhydride,4-sulfo-phthalic acid, 4-sulfo-phenyl-3,5-dicarbomethoxybenzene,6-sulfo-2-naphthyl-3,5-dicarbomethoxybenzene, sulfo-terephthalic acid,dimethyl-sulfo-terephthalate, dialkyl-sulfo-terephthalate,sulfo-ethanediol, 2-sulfo-propanediol, 2-sulfo-butanediol,3-sulfopentanediol, 2-sulfo-hexanediol, 3-sulfo-2-methylpentanediol,N,N-bis(2-hydroxyethyl)-2-aminoethane sulfonate, or2-sulfo-3,3-dimethylpentanediol, sulfo-p-hydroxybenzoic acid; a toner asrepresented by the following chemically bonded random segments

wherein the segments m, n and o represent the random units of thepolymer and wherein the sum of m, n, and o is from about 500 to about4,000; p represents the repeating segment of the polydimethylsiloxaneand is from about 1,000 to about 7,000 units; R is an alkylene; R′ is analkali arylenesulfonate of phenylenesulfonate,isophthalylene-5-sulfonate, terephthalylene-sulfonatephthalylene-sulfonate, or an alkali alkylene-sulfonate ofpropylene-sulfonate, butylene-sulfonate, pentylene-sulfonate,hexylene-sulfonate of the formulas

wherein a and b are numbers of from about 1 to about 4, and M ishydrogen, an alkali (I) metal of lithium, sodium, potassium, rubidium,cesium, an alkali (II) metal of beryllium, magnesium, calcium, strontiumor barium, a metal of (II), iron (III), aluminum (III), or copper (I),and R″ is ethylene, propylene or butylene; a toner wherein the polyestersiloxane is selected from the group consisting of copoly(1,2-propyleneterephthalate-co-diethylene terephthalate)-copoly(1,2-propylene5-sulfoisophthalate-co-diethylene 5-sulfo-isophthalate)-copolydimethylsiloxane, copoly(dipropylene terephthalate-co-diethyleneterephthalate)-copoly(dipropylene 5-sulfoisophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethyl siloxane, copoly(1,2-propyleneterephthalate)-copoly(1,2-propylene5-sulfoisophthalate)-copolydimethylsiloxane, and copoly(dipropyleneterephthalate)-copoly(dipropylene 5-sulfoisophthalate)-copolydimethylsiloxane or mixtures thereof; a toner comprised of a colorant and asulfonated polyester siloxane copolymer resin generated from thereaction of an organic diol monomer, an organic diacid monomer, acarbinol carboxy terminated polydimethylsiloxane, and at least one ionsalt of a sulfonate difunctional monomer; a toner comprised of acolorant and sulfonated polyester siloxane copolymer resin generatedfrom the reaction of an organic diol monomer, an organic diestermonomer, a carbinol carboxy terminated polydimethylsiloxane, and a saltof a sulfonate difunctional monomer; a developer comprised of the tonerillustrated herein and carder; a developer wherein the carrier iscomprised of a core and a coating thereover; a developer wherein thecarrier is comprised of a ferrite; a developer wherein the carrier iscomprised of a core with at least one polymer coating thereover; a tonerwherein there is selected an organic diacid monomer; a toner whereinthere is selected a diester monomer; a toner wherein the polyestersiloxane is copoly(1,2-propylene terephthalate-co-diethyleneterephthalate)-copoly(1,2-propylene 5-sulfoisophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethyl siloxane; polyester-siloxanecopolymer backbones with an ionic or a hydrophilic hydrogen sulfonateand metalized sulfonate groups, and wherein the metal is, for example,zinc, copper, manganese, chromium, iron, zirconium or an alkali metal,such as sodium, lithium, potassium, rubidium cesium, beryllium,magnesium, calcium, strontium, barium or mixtures thereof.

Examples of the polyester-siloxane include copoly(1,2-propyleneterephthalate-co-diethylene terephthalate)-copoly(1,2-propylene5-sulfoisophthalate-co-diethylene 5-sulfo-isophthalate)-copolydimethylsiloxane, copoly(dipropylene terephthalate-co-diethyleneterephthalate)-copoly(dipropylene 5-sulfoisophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethylsiloxane, copoly(1,2-propyleneterephthalate)-copoly(1,2-propylene5-sulfoisophthalate)-copolydimethylsiloxane, copoly(dipropyleneterephthalate)-copoly(dipropylene 5-sulfoisophthalate)-copolydimethylsiloxane, copoly(ethylene terephthalate)-copoly(ethylene5-sulfoisophthalate)-copolydimethylsiloxane, copoly(butylleneterephthalate)-copoly(butyllene5-sulfoisophthalate)-copolydimethylsiloxane, and copoly(1,3-propyleneterephthalate)-copoly(1,3-propylene5-sulfoisophthalate)-copolydimethylsiloxane, and the like; and whereinthe polyester-siloxanes can be characterized by gel permeationchromatography and with, for example, a weight average molecular weightof from about 5,000 to about 500,000 and preferably from about 5,000 toabout 100,000 grams per mole; a number average molecular weight of fromabout 2,000 to about 100,000, and more specifically, from about 2,500 toabout 50,000 grams per mole; and a polydispersity of from about 2 to 30,and more specifically, from about 2 to about 15.

The sulfo-polyester-siloxane resins can be prepared from a suitableselection of monomers, which result in the polyester portion of thesulfo-polyester-siloxane resin that displays, for example, a glasstransition temperature of from about 10° C. to about 100° C., andwherein the polydimethylsiloxane portion of the copolymer displays aglass transition temperature of from about −78° C. to about −20° C. withrespect to the sulfo-polyester-siloxane resins; and wherein withsulfo-polyester-siloxane resin with the appropriate selection ofmonomers can display a molecular weight, M_(w) of from about 5,000 gramsper mole to about 500,000 grams per mole, a number average molecularweight of from about 2,500 grams per mole to about 300,000 grams permole, and a polydispersity of from about 2 to about 100 as measured bygel permeation chromatography, and preferably a molecular weight, M_(w)of from about 5,000 grams per mole to about 100,000 grams per mole, anumber average molecular weight of from about 2,500 grams per mole toabout 50,000 grams per mole, and a polydispersity of from about 2 toabout 10.

In embodiments the sulfopolyestersiloxane resin, such ascopoly(1,2-propylene-5-sulfoisophthalate sodiosalt)-copoly(1,2-propylene terephthalate-co-diethyleneterephthalate)-copoly-dimethylsiloxane, can be prepared by charging a 1liter Parr reactor equipped with a mechanical stirrer and side condenserwith a mixture of from about 0.10 mole to about 0.2, and morespecifically, 0.10 mole to about 0.15 mole of a carbinol terminatedpolydimethylsiloxane PS554, available from United Chemical Technologies;from about 0.8 to about 0.95 mole, and more specifically, from about 0.9to about 0.95 mole of diester, such as dimethylterephthalate; from about0.05 to about 0.05 mole, and more specifically, 0.025 to about 0.05 moleof sulfonate monomer, such as dimethyl 5-sulfo-isophthalate sodio salt;from about 1.5 moles to about 1.95 moles, and more specifically, fromabout 1.75 moles to about 1.85 moles of a diol, such as 1,2-propanediolor diethylene glycol or a mixture of the diols, and containing fromabout 0.15 to about 0.3 mole, and more specifically, from about 0.15 toabout 0.3 mole of diethylene glycol, and from about 0.01 to about 0.001mole, and more specifically, from about 0.02 to about 0.05 mole of acondensation catalyst, such as butyltin oxide hydroxide. The reactor issubsequently heated, for example, to 170° C. for a suitable duration of,for example, from about 360 minutes to about 720 minutes with stirringat, for example, from about 10 revolutions per minute to about 200revolutions per minute. During this time, from about 1.7 moles to about1.9 moles of methanol byproduct can be collected through the condenser.The reactor temperature is then increased to about 220° C. and thepressure is reduced from 760 Torr to about 1 Torr over a period of fromabout 2 hours to about 3 hours. The polymeric resin product comprised ofcopoly(1,2-propylene-5-sulfoisophthalate sodio salt)-poly(1,2-propyleneterephthalate-co-diethylene terephthalate)-copolydimethylsiloxane, canthen be discharged through the bottom of the reactor and cooled to roomtemperature, about 22° C. to about 25° C. The product is then identifiedby physical analysis, such as differential scanning calorimetry, gelpermeation chromatography, and rheology.

Specific examples of diols selected for the preparation of the sulfopolyester-siloxanes include various known diols, such as ethyleneglycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol,1,3-butylene glycol, 1,4-butylene glycol, 1,2-pentylene glycol,1,3-pentylene glycol, 1,4-pentylene glycol, 1,5-pentylene glycol,1,2-hexylene glycol, 1,3-hexylene glycol, 1,4-hexylene glycol,1,5-hexylene glycol, 1,6-hexylene glycol, heptylene glycols, octyleneglycols, decylene glycol, dodecylene glycol, 2,2-dimethyl propanediol,propoxylated bisphenol A, ethoxylated bisphenol A, 1,4-cyclohexane diol,1,3-cyclohexane diol, 1,2-cyclohexane diol, 1,2-cyclohexane dimethanol,mixtures thereof, and the like; and wherein the diol can be selected,for example, in various effective amounts of, for example, from about 45to about 55 mole, and more specifically, from about 49 to about 51percent of the polyester product resin.

Examples of diacids or diesters selected for the preparation of thesulfo polyester-siloxanes include malonic acid, succinic acid,2-methylsuccinic acid, 2,3-dimethylsuccinic acid, dodecylsuccinic acid,glutaric acid, adipic acid, 2-methyladipic acid, pimelic acid, azelaicacid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid,1,2-cyclohexanedioic acid, 1,3-cyclohexanedioic acid,1,4-cyclohexanedioic acid, glutaric anhydride, succinic anhydride,dodecylsuccinic anhydride, maleic anhydride, fumaric acid, maleic acid,itaconic acid, 2-methyl itaconic acid, and dialkyl esters, such as themethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl esters ofabove mentioned acids. The alkyl groups of the dialkyl ester possessfrom about one carbon atom to about 5 carbon atoms, and mixturesthereof, and the like, and which component is employed, for example, inamounts of from about 45 to about 55, and more specifically, from about48 to about 51 mole percent of the resin.

Examples of polycondensation catalysts selected include tetraalkyltitanates, dialkyltin oxide such as dibutyltin oxide, tetraalkyltin suchas dibutyltin dilaurate, dialkyltin oxide hydroxide such as butyltinoxide hydroxide, aluminum alkoxides, alkyl zinc, dialkyl zinc, zincoxide, stannous oxide, or mixtures thereof; and which catalysts areselected in effective amounts of from, for example, about 0.5 to 2 molepercent, 0.01 mole percent to about 5 mole percent based on the startingdiacid or diester used to generate the polyester resin.

Hydrophilic monomer examples, which can be selected for the preparationof the sulfo polyester-siloxane resin, include the ion salts ofsulfonated difunctional monomers wherein the ion is an alkali oralkaline earth, such as lithium, sodium, potassium, cesium, rubidium,magnesium, barium, calcium or beryllium and the like, and the sulfonateddifunctional moiety is selected from the group consisting ofdimethyl-5-sulfo-isophthalate,dialkyl-5-sulfo-isophthalate-4-sulfo-1,8-naphthalic anhydride,4-sulfo-phthalic acid, 4-sulfophenyl-3,5-dicarbomethoxybenzene,6-sulfo-2-naphthyl-3,5-dicarbomethoxybenzene, sulfo-terephthalic acid,dimethyl-sulfo-terephthalate, dialkyl-sulfo-terephthalate,sulfo-ethanediol, 2-sulfo-propanediol, 2-sulfo-butanediol,3-sulfopentanediol, 2-sulfo-hexanediol, 3-sulfo-2-methylpentanediol,N,N-bis(2-hydroxyethyl)-2-aminoethane sulfonate,2-sulfo-3,3-dimethylpentanediol, sulfo-p-hydroxybenzoic acid, mixturesthereof and the like. Effective hydrophilic amounts of, for example,from about 0.1 to about 5 weight percent, and more specifically, fromabout 2 to about 4 weight percent of the resin can be selected.

Additionally, crosslinking or branching agents can be utilized in theprocess of preparation, such as trifunctional or multifunctionalmonomers, which agents usually increase the molecular weight andpolydispersity of the polyester, and which agents are selected from thegroup consisting of glycerol, trimethylol ethane, trimethylol propane,pentaerythritol, sorbitol, diglycerol, trimellitic acid, trimelliticanhydride, pyromellitic acid, pyromellitic anhydride,1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylicacid, 1,2,4-butanetricarboxylic acid, mixtures thereof, and the like;and which agents or components can be selected in effective amounts offrom, for example, about 0.1 to about 6 mole percent, and morespecifically, about 0.5 to about 4 mole percent based on the startingdiacid or diester used to generate the resin.

Polydimethylsiloxane prepolymers that can be selected for thepreparation of the sulfo polyester-siloxane resins include carbinolterminated polydimethylsiloxane, such asbis-(1,3-hydroxypropyl)-polydimethylsiloxane,bis-(1,3-hydroxyethyl)-polydimethylsiloxane, andbis-(1,3-hydroxybutyl)-polydimethylsiloxane, or carboxyl terminatedpolydimethylsiloxane, such asbis-(1,3-carboxypropyl)-polydimethylsiloxane,bis-(1,3-carboxyethyl)-polydimethylsiloxane, and which prepolymer can beselected in effective amounts of, for example, from about 5 to about 30mole percent, and more specifically, from about 10 to about 25 molepercent based on the starting diacid or diester used to generate theresins.

The resins illustrated herein can be selected as toners and coatings;examples of toners include the resin, colorant, and know additives.

The following Examples are being supplied to further define variousspecies of the present invention, it being noted that these Examples areintended to illustrate and not limit the scope of the present invention.Parts and percentages are by weight, temperatures are in degreesCentigrade, and g represents grams unless otherwise indicated.

EXAMPLE I

There was prepared copoly(1,2-propylene terephthalate-co-diethyleneterephthalate)-copoly(1,2-propylene 5-sulfo-isophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethylsiloxane derived from propyleneglycol, diethylene glycol, dimethyl terephthalate, sodio dimethyl5-sulfoisophthalate, and 15 weight percent of carbinol terminatedpolydimethylsiloxane.

A 1 liter Parr reactor equipped with a bottom drain valve, a doubleturbine agitator and a distillation receiver with a cold water condenserwas charged with 313 grams of dimethylterephthalate, 38 grams ofdimethyl 5-sulfo isophthalate sodium salt, 250 grams of 1,2-propanediol,37.5 grams of diethylene glycol, 67 grams ofbis-(1,3-hydroxypropyl)polydimethylsiloxane available as a carbinolterminated polydimethylsiloxane 563 with viscosity of about 300 to about350 centistokes and available from United Chemical Technologies, and 1gram of butyltin oxide catalyst obtained as FASCAT 4100™ from ElfAtochem North America, Inc. The reactor was then heated to 165° C.(degrees Centigrade) with stirring at 150 revolutions per minute andthen heated to 200° C. over a duration of 6 hours wherein a methanolbyproduct was collected, via the distillation receiver, in a container,and which byproduct was comprised of about 98 percent by volume ofmethanol and 2 percent by volume of 1,2-propanediol as measured by theABBE refractometer available from American Optical Corporation. Thereactor mixture was then maintained at 200° C., and the pressure wasreduced from atmospheric to about 0.2 Torr over a duration of about 3hours. During this time of 3 hours, there were collected 120 grams ofglycol containing about 97 percent by volume of 1,2-propanediol and 3percent by volume of methanol as measured by the ABBE refractometer. Thereactor was then purged with nitrogen to atmospheric pressure, and thepolymer was discharged through the bottom drain onto a container cooledwith dry ice to yield 485 grams of copoly(1,2-propyleneterephthalate-co-diethylene terephthalate)-copoly(1,2-propylene5-sulfoisophthalate-co-diethylene 5-sulfo-isophthalate)-copolydimethylsiloxane.

The above resulting resin product glass transition temperature wasmeasured to be 53° C. (onset) utilizing the 910 Differential ScanningCalorimeter available from E. I. DuPont operating at a heating rate of10° C. per minute. For the polyester resin of this Example, a softeningpoint of 131.2° C. was obtained using a Mettler Flow tester.

EXAMPLE II

There was prepared copoly(1,2-propylene terephthalate-co-diethyleneterephthalate)-copoly(1,2-propylene 5-sulfo-isophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethylsiloxane derived from propyleneglycol, diethylene glycol, dimethyl terephthalate, sodio dimethyl5-sulfoisophthalate, and 15 weight percent of a carbinol terminatedpolydimethylsiloxane.

A 1 liter Parr reactor equipped with a bottom drain valve, doubleturbine agitator and distillation receiver with a cold water condenserwas charged with 313 grams of dimethylterephthalate, 38 grams ofdimethyl 5-sulfo isophthalate sodium salt, 250 grams of 1,2-propanediol,37.5 grams of diethylene glycol, 67 grams ofbis-(1,3-hydroxypropyl)polydimethylsiloxane available as Carbinolterminated polydimethylsiloxane 563 with viscosity of about 300 to about350 centistokes and available from United Chemical Technologies, and 1gram of butyltin oxide catalyst obtained as FASCAT 4100™ from ElfAtochem North America, Inc. The reactor was then heated to 165° C. withstirring at 150 revolutions per minute and then heated to 200° C. over aduration of 6 hours, wherein a methanol byproduct was collected in acontainer via the distillation receiver, and which byproduct wascomprised of about 98 percent by volume of methanol and 2 percent byvolume of 1,2-propanediol as measured by a ABBE refractometer availablefrom American Optical Corporation. The reactor mixture was thenmaintained at 200° C., and the pressure was reduced from atmospheric toabout 0.2 Torr over a duration of about 3 hours. During this time of 3hours, there were collected 120 grams of glycol containing about 97percent by volume of 1,2-propanediol and 3 percent by volume of methanolas measured by the ABBE refractometer. The reactor was then purged withnitrogen to atmospheric pressure, and the polymer discharged through thebottom drain onto a container cooled with dry ice to yield 485 grams ofcopoly(1,2-propylene terephthalate-co-diethyleneterephthalate)-copoly(1,2-propylene 5-sulfoisophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethyl siloxane.

The above resulting resin product glass transition temperature wasmeasured to be 61.8° C. (onset) utilizing the 910 Differential ScanningCalorimeter available from E. I. DuPont operating at a heating rate of10° C. per minute. For the polyester resin of this Example, a softeningpoint of 150.9° C. was obtained as measured with a known Mettler Flowtester.

EXAMPLE III

There was prepared poly(1,2-propylene terephthalate-co-diethyleneterephthalate)-copoly(1,2-propylene 5-sulfo-isophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethylsiloxane derived from propyleneglycol, diethylene glycol, dimethyl terephthalate, sodio dimethyl5-sulfoisophthalate, and 10 weight percent of Carbinol terminatedpolydimethylsiloxane.

A 1 liter Parr reactor equipped with a bottom drain valve, doubleturbine agitator and distillation receiver with a cold water condenserwas charged with 313 grams of dimethylterephthalate, 38 grams ofdimethyl 5-sulfo isophthalate sodium salt, 250 grams of 1,2-propanediol,37.5 grams of diethylene glycol, 45.8 grams ofbis-(1,3-hydroxypropyl)polydimethylsiloxane available as carbinolterminated pblydimethylsiloxane 563 with viscosity of about 300 to about350 centistokes and available from United Chemical Technologies, and 1gram of butyltin oxide catalyst obtained as FASCAT 4100™ from ElfAtochem North America, Inc. The reactor was then heated to 165° C. withstirring at 150 revolutions per minute and then heated to 200° C. over aduration of 6 hours, wherein a methanol byproduct was collected via thedistillation receiver to a container, and which byproduct was comprisedof about 98 percent by volume of methanol and 2 percent by volume of1,2-propanediol as measured by the ABBE refractometer available fromAmerican Optical Corporation. The reactor mixture was then maintained at200° C., and the pressure was reduced from atmospheric to about 0.2 Torrover a duration of about 3 hours. During this time of 3 hours, therewere collected 120 grams of glycol containing about 97 percent by volumeof 1,2-propanediol and 3 percent by volume of methanol as measured bythe ABBE refractometer. The reactor was then purged with nitrogen toatmospheric pressure, and the polymer discharged through the bottomdrain onto a container cooled with dry ice to yield 485 grams ofcopoly(1,2-propylene terephthalate-co-diethyleneterephthalate)-copoly(1,2-propylene 5-sulfoisophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethyl siloxane.

The above resulting resin product glass transition temperature wasmeasured to be 55.2° C. (onset) utilizing the 910 Differential ScanningCalorimeter available from E. I. DuPont operating at a heating rate of10° C. per minute. For the polyester resin of this Example, a softeningpoint of 136.8° C. was measured using the Mettler Flow tester.

EXAMPLE IV

There was prepared copoly(1,2-propylene terephthalate-co-diethyleneterephthalate)-copoly(1,2-propylene 5-sulfo-isophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethylsiloxane derived from propyleneglycol, diethylene glycol, dimethyl terephthalate, sodio dimethyl5-sulfoisophthalate, and 10 weight percent of Carbinol terminatedpolydimethylsiloxane.

A 1 liter Parr reactor equipped with a bottom drain valve, doubleturbine agitator and distillation receiver with a cold water condenserwas charged with 313 grams of dimethylterephthalate, 38 grams ofdimethyl 5-sulfo isophthalate sodium salt, 250 grams of 1,2-propanediol,37.5 grams of diethylene glycol, 45 grams ofbis-(1,3-hydroxypropyl)polydimethylsiloxane available as Carbinolterminated polydimethylsiloxane 563 with viscosity of about 300 to about350 centistokes and available from United Chemical Technologies, and 1gram of butyltin oxide catalyst obtained as FASCAT 4100™ from ElfAtochem North America, Inc. The reactor was then heated to 165° C. withstirring at 150 revolutions per minute and then heated to 200° C. over aduration of 6 hours, wherein a methanol byproduct was collected to acontainer via the distillation receiver, and which byproduct wascomprised of about 98 percent by volume of methanol and 2 percent byvolume of 1,2-propanediol as measured by the ABBE refractometeravailable from American Optical Corporation. The reactor mixture wasthen maintained at 200° C., and the pressure was reduced fromatmospheric to about 0.2 Torr over a duration of about 3 hours. Duringthis time of 3 hours, there were collected 120 grams of glycolcontaining about 97 percent by volume of 1,2-propanediol and 3 percentby volume of methanol as measured by the ABBE refractometer. The reactorwas then purged with nitrogen to atmospheric pressure, and the polymerdischarged through the bottom drain onto a container cooled with dry iceto yield 485 grams of copoly(1,2-propylene terephthalate-co-diethyleneterephthalate)-copoly(1,2-propylene 5-sulfoisophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethyl siloxane.

The above resulting resin product glass transition temperature wasmeasured to be 63.6° C. (onset) utilizing the 910 Differential ScanningCalorimeter available from E. I. DuPont operating at a heating rate of10° C. per minute. For the polyester resin of this Example a softeningpoint of 154.1° C. was measured using the Mettler Flow tester.

EXAMPLE V

There was prepared copoly(1,2-propylene terephthalate-co-diethyleneterephthalate)-copoly(1,2-propylene 5-sulfo-isophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethylsiloxane derived from propyleneglycol, diethylene glycol, dimethyl terephthalate, sodio dimethyl5-sulfoisophthalate, and 5 weight percent of a Carbinol terminatedpolydimethylsiloxane.

A 1 liter Parr reactor equipped with a bottom drain valve, doubleturbine agitator and distillation receiver with a cold water condenserwas charged with 313 grams of dimethylterephthalate, 38 grams ofdimethyl 5-sulfo isophthalate sodium salt, 250 grams of 1,2-propanediol,37.5 grams of diethylene glycol, 23 grams ofbis-(1,3-hydroxypropyl)polydimethylsiloxane available as Carbinolterminated polydimethylsiloxane 563 with viscosity of about 300 to about350 centistokes and available from United Chemical Technologies, and 1gram of butyltin oxide catalyst obtained as FASCAT 4100™ from ElfAtochem North America, Inc. The reactor was then heated to 165° C. withstirring at 150 revolutions per minute and then heated to 200° C. over aduration of 6 hours, wherein a methanol byproduct was collected via thedistillation receiver to a container, and which byproduct was comprisedof about 98 percent by volume of methanol and 2 percent by volume of1,2-propanediol as measured by the ABBE refractometer available fromAmerican Optical Corporation. The reactor mixture was then maintained at200° C., and the pressure was reduced from atmospheric to about 0.2 Torrover a duration of about 3 hours. During this time of 3 hours, therewere collected 120 grams of glycol containing about 97 percent by volumeof 1,2-propanediol and 3 percent by volume of methanol as measured bythe ABBE refractometer. The reactor was then purged with nitrogen toatmospheric pressure, and the polymer discharged through the bottomdrain onto a container cooled with dry ice to yield 485 grams ofcopoly(1,2-propylene terephthalate-co-diethyleneterephthalate)-copoly(1,2-propylene 5-sulfoisophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethyl siloxane.

The above resulting resin product glass transition temperature wasmeasured to be 64.7° C. (onset) utilizing the 910 Differential ScanningCalorimeter available from E. I. DuPont operating at a heating rate of10° C. per minute. For the polyester resin of this Example, a softeningpoint of 143° C. was obtained using the Mettler Flow tester.

EXAMPLE VI

There was prepared copoly(1,2-propylene terephthalate-co-diethyleneterephthalate)-copoly(1,2-propylene 5-sulfo-isophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethylsiloxane derived from propyleneglycol, diethylene glycol, dimethyl terephthalate, sodio dimethyl5-sulfoisophthalate, and 5 weight percent of Carbinol terminatedpolydimethylsiloxane.

A 1 liter Parr reactor equipped with a bottom drain valve, doubleturbine agitator and distillation receiver with a cold water condenserwas charged with 313 grams of dimethylterephthalate, 38 grams ofdimethyl 5-sulfo isophthalate sodium salt, 250 grams of 1,2-propanediol,37.5 grams of diethylene glycol, 23bis-(1,3-hydroxypropyl)polydimethylsiloxane available as Carbinolterminated polydimethylsiloxane 563 with viscosity of about 300 to about350 centistoke and available from United Chemical Technologies, and 1gram of butyltin oxide catalyst obtained as FASCAT 4100™ from ElfAtochem North America, Inc. The reactor was then heated to 165° C. withstirring at 150 revolutions per minute and then heated to 200° C. over aduration of 6 hours, wherein a methanol byproduct was collected to acontainer via the distillation receiver, and which byproduct wascomprised of about 98 percent by volume of methanol and 2 percent byvolume of 1,2-propanediol as measured by the ABBE refractometeravailable from American Optical Corporation. The reactor mixture wasthen maintained at 200° C., and the pressure was reduced fromatmospheric to about 0.2 Torr over a duration of about 3 hours. Duringthis time of 3 hours, there were collected 120 grams of glycolcontaining about 97 percent by volume of 1,2-propanediol and 3 percentby volume of methanol as measured by the ABBE refractometer. The reactorwas then purged with nitrogen to atmospheric pressure, and the polymerdischarged through the bottom drain onto a container cooled with dry iceto yield 485 grams of copoly(1,2-propylene terephthalate-co-diethyleneterephthalate)-copoly(1,2-propylene 5-sulfoisophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethyl siloxane.

The above resulting resin/polymer product glass transition temperaturewas measured to be 63.7° C. (onset) utilizing the 910 DifferentialScanning Calorimeter available from E. I. DuPont operating at a heatingrate of 10° C. per minute. For the polyester resin of this Example asoftening point of 140° C. was measured with the Mettler Flow tester.

EXAMPLES VII TO XII

Each of the above prepared sulfo polyester-siloxane resins weredispersed in water at about 85° C. to about 95° C. with agitation toprovide a stable emulsion, that is, for example, the emulsion siloxanepolymer diameter size did not substantially change in composition orproperties on storing over extended time periods, such as two weeks. Thesolids loading of the emulsions were about 76 percent by weight of resinand about 24 percent by weight of water. The particle size of the resinin the emulsion latex was then measured utilizing the Nincomp Particlesize analyzer. Typically, a bimodal or trimodal distribution of particlesizes were obtained, and the peaks thereof are recited in Table A. Thevalues in the table refer to the measured resin emulsion size diameters.

TABLE A EX. RESIN EMULSION SIZES VII Exam- 32% at 11.0 nm 66% at 34.9 nm2% at 154.6 nm ple I VIII Exam- 83.6% at 48 nm 14.3% at 111 nm 2% at193.6 nm ple II IX Exam- 99.8% at 32 nm 0.2% 160.7 nm ple III X Exam-99.7% 32.0 nm 0.3% at 164.7 ple IV XI Exam- 100.00% at 43.8 nm ple V XIIExam- 51.5% at 23.6 nm 48.5% at 47.0 nm ple VI

Toner Preparation

Although toners can be prepared by the conventional extrusion andjetting process, since these resins are emulsifiable in water, anemulsion coalescence route was selected.

EXAMPLES XIII TO XVIII

Six toners comprised of 4 percent (percent by weight) of a cyan pigment,available from Sun Chemicals as FLEXIVERSE PB 15:3™, and 96 percent byweight of the sulfopolyester-siloxanes of Examples I to VI were preparedby the following procedure; tabulated in Table B are the toners measuredrespective particle size, GSD and glass transition temperature.

To a 4 liter glass kettle equipped with a mechanical stirrer and heatingmantle were added 2.4 liters of a 10 percent by weight of thesulfopolyester-siloxane emulsion of Examples I to VI (Table B), and22.85 grams of cyan pigment, available as a 42 percent pigmentdispersion in water and obtained from Sun Chemicals as FLEXIVERSE PB15:3™. The resulting mixture was then heated to 56° C. and stirred at250 revolutions per minute. To this was then added using a pump and overa 5 hour period 1 liter of an aqueous solution comprised of 5 percent byweight of zinc acetate. The mixture resulting was then heated at 56° C.for an additional 2 hours, and then left to cool to room temperature,about 22° C. to 25° C., overnight, about 18 to about 20 hours. The tonerproduct was then filtered off, and washed two times by re-suspending itin 4 liters of water; stirred for 2 hours and refiltered. The filteredtoner products were then dried using a fluid bed drier. Each of the drytoners were then characterized by a differential scanning calorimeter.

TABLE B CYAN TONERS TONER RESIN P.S. GSD Tg (onset) Example XIII ExampleI 6.09 1.25 63.6 Example XIV Example II 7.21 1.25 55.8 Example XVExample III 5.94 1.22 59.5 Example XVI Example IV 6.66 1.21 62.4 ExampleXVII Example V 5.69 1.23 65.6 Example XVIII Example VI 6.21 1.21 65.9

Unfused images were generated with the above toners on Xerox ColourExpression (CX) paper. Excellent images were achieved with a developercomprised of the above toners and a Xerox carrier 9700MICR comprised of,for example, a core of iron or steel, and thereover a coating of apolymethyl methacrylate, 40 weight percent, and polyvinylidene fluoride,60 weight percent, and wherein the toners had added thereto 4 percentsilica, available as AEROSIL™ from Degussa Chemicals, 2.3 percent byweight of titanium oxide SMT5103™ and 0.3 percent of zinc stearate.

The images were then fused using the Xerox DC2006 printer which containsno oil on the fuser rolls. The toners of Examples XIII to XVIIIdisplayed hot offset temperatures (HOT) between about 150° C. and about160° C.; acceptable gloss, for example about or in excess of 50 ggu(Gardener gloss units), was achieved, the minimum fix temperatures wasabout 135° C. to about 140° C. for all toners.

Other embodiments and modifications of the present invention may occurto those skilled in the art subsequent to a review of the informationpresented herein; these embodiments and modifications, equivalentsthereof, substantial equivalents thereof, or similar equivalents thereofare also included within the scope of this invention.

What is claimed is:
 1. A toner comprised of colorant and a sulfonatedpolyester-siloxane polymer generated from the reaction of at least oneorganic diol monomer, at least one organic diacid or at least onediester monomer, at least one carbinol carboxy terminated polydimethylsiloxane, and at least one ion salt of a sulfonate difunctional monomer.2. A toner in accordance with claim 1 wherein said colorant is apigment.
 3. A toner in accordance with claim 1 wherein said colorant isa dye.
 4. A toner in accordance with claim 1 wherein said colorant iscomprised of a mixture of a pigment and a dye.
 5. A toner in accordancewith claim 1 wherein said polymer is copoly(1,2-propyleneterephthalate-co-diethylene terephthalate)-copoly(1,2-propylene5-sulfoisophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethylsiloxane, copoly(dipropyleneterephthalate-co-diethylene terephthalate)-copoly(dipropylene5-sulfoisophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethylsiloxane, copoly(1,2-propyleneterephthalate)-copoly(1,2-propylene5-sulfoisophthalate)-copolydimethylsiloxane, and copoly(dipropyleneterephthalate)-copoly(dipropylene5-sulfoisophthalate)-copolydimethylsiloxane.
 6. A toner in accordancewith claim 1 wherein said polymer is represented by the followingrandomly chemically attached segments

wherein the segments m, n and o represent the random units of thepolymer and wherein the sum of m, n, and o is from about 10 to about10,000; p represents the repeating segment of the polydimethyl siloxane,and is from about 100 to about 10,000 units; R is an alkylene; R′ is ahydrogen atom, an alkali arylenesulfonate or an alkalialkylene-sulfonate, and R″ is an alkylene.
 7. A toner in accordance withclaim 6 wherein said alkylene contains from about 1 to about 18 carbonatoms; and said oxyalkylene possesses a carbon chain length of fromabout 2 to about 36 carbon atoms.
 8. A toner in accordance with claim 2wherein R′ is an alkali arylene sulfonate or an alkali alkylenesulfonate of the formulas

wherein a and b are numbers of from about 1 to about 5, and M ishydrogen, an alkali metal of lithium, sodium, potassium, rubidium,cesium, beryllium, magnesium, calcium, strontium and barium, or a metalof zinc (II), iron (III), aluminum (III), or copper (I).
 9. A toner inaccordance with claim 8 wherein the ion salt of the sulfonatedifunctional monomer is the hydrogen, lithium, sodium, potassium,cesium, rubidium, magnesium, barium, calcium or beryllium, zinc,zirconium, vanadium, copper, or aluminum salt ofdimethyl-5-sulfo-isophthalate,dialkyl-5-sulfo-isophthalate4-sulfo-1,8-naphthalic anhydride,4-sulfo-phthalic acid, 4sulfo-phenyl-3,5-dicarbomethoxybenzene,6-sulfo-2-naphthyl-3,5-dicarbomethoxybenzene, sulfo-terephthalic acid,dimethyl-sulfo-terephthalate, dialkyl-sulfo-terephthalate,sulfo-ethanediol, 2-sulfo-propanediol, 2-sulfo-butanediol,3sulfopentanediol, 2-sulfo-hexanediol, 3-sulfo-2-methylpentanediol,N,N-bis(2-hydroxyethyl)-2-aminoethane sulfonate, or2-sulfo-3,3-dimethylpentanediol, sulfo-p-hydroxybenzoic acid.
 10. Atoner in accordance with claim 2 as represented by the followingchemically bonded random segments

wherein the segments m, n and o represent the random units of thepolymer and wherein the sum of m, n, and o is from about 500 to about4,000; p represents the repeating segment of the polydimethylsiloxaneand is from about 1,000 to about 7,000 units; R is an alkylene; R′ is analkali arylenesulfonate of phenylenesulfonate,isophthalylene-5-sulfonate, terephthalylene-sulfonatephthalylene-sulfonate, or an alkali alkylene-sulfonate ofpropylene-sulfonate, butylene-sulfonate, pentylene-sulfonate,hexylene-sulfonate of the formulas

wherein a and b are numbers of from about 1 to about 4, and M ishydrogen, an alkali (I) metal of lithium, sodium, potassium, rubidium,cesium, an alkali (II) metal of beryllium, magnesium, calcium, strontiumor barium, a metal of (II), iron (III), aluminum (III), or copper (I),and R″ is ethylene, propylene or butylene.
 11. A toner in accordancewith claim 1 wherein said polyester siloxane is selected from the groupconsisting of copoly(1,2-propylene terephthalate-co-diethyleneterephthalate)-copoly(1,2-propylene 5-sulfoisophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethyl siloxane, copoly(dipropyleneterephthalate-co-diethylene terephthalate)-copoly(dipropylene5-sulfoisophthalate-co-diethylene5-sulfo-isophthalate)-copolydimethylsiloxane, copoly(1,2-propyleneterephthalate)-copoly(1,2-propylene5-sulfoisophthalate)-copolydimethylsiloxane, and copoly(dipropyleneterephthalate)-copoly(dipropylene5-sulfoisophthalate)-copolydimethylsiloxane.
 12. A toner comprised of acolorant and a sulfonated polyester siloxane copolymer resin generatedfrom the reaction of at least one organic diol monomer, at least oneorganic diacid monomer, at least one carbinol carboxy terminatedpolydimethylsiloxane, and at least one ion salt of a sulfonatedifunctional monomer.
 13. A toner comprised of a colorant and sulfonatedpolyester siloxane copolymer resin generated from the reaction of anorganic diol monomer, an organic diester monomer, a carbinol carboxyterminated polydimethylsiloxane, and an ion salt of a sulfonatedifunctional monomer.
 14. A toner in accordance with claim 1 wherein atleast one is from 1 to about
 25. 15. A toner in accordance with claim 1wherein at least one is from 1 to about
 10. 16. A toner in accordancewith claim 1 wherein at least one is from 1 to about
 5. 17. A developercomprised of the toner of claim 1 and carrier.
 18. A developer inaccordance with claim 17 wherein said carrier is comprised of a core anda coating thereover.
 19. A developer in accordance with claim 17 whereinsaid carrier is comprised of a ferrite.
 20. A developer in accordancewith claim 17 wherein said carrier is comprised of a core with at leastone polymer coating thereover.
 21. A developer in accordance with claim20 wherein at least one is from about 1 to about
 5. 22. A toner inaccordance with claim 1 wherein there is selected an organic diacidmonomer.
 23. A toner in accordance with claim 1 wherein there isselected a diester monomer.
 24. A toner in accordance with claim 1wherein said polyester siloxane is copoly(1,2-propyleneterephthalate-co-diethylene terephthalate)-copoly(1,2-propylene5-sulfoisophthalate-co-diethylene 5-sulfo-isophthalate)-copolydimethylsiloxane.
 25. A toner consisting essentially of a colorant and asulfonated polyester siloxane polymer.